SYNTHESIS OF TERT-ALKYLPEROXY-SUBSTITUTED DERIVATIVES
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phenylglycidol (XI) lacking peroxy group]. The chemical
shifts of protons attached to C2 atom in the fragment C
CHOHC essentially depend on the alkoxy substituents
at the atoms C1 and C3. For instance, in epoxyperoxide I
and in glycidol, i.e., in compounds containing an epoxy
ring, the signal of the proton belonging to the mentioned
group appears in a relatively strong field (d ~3.25 and
~3.38 ppm). In noncyclic compounds, namely, in 1-mono-
and 1,3-disubstituted glycerols this proton signal is
displaced downfield ((d ~3.8 ppm for compounds IV and
Ve, and ~4.1 ppm for compound Va). The position of the
signals from the methylene protons which prior to the
addition reaction were included into the epoxy ring (H1)
depends mainly on the character of the alkyl substituent
at the oxygen atom linked to this methylene group. The
characteristic feature of these signals is the magnetic
nonequivalence of these protons that is also observed
for the protons of the methylene group in the
CH2OC(CH3)3 moiety.
was added dropwise within 3040 min 0.05 mol of
peroxide Ia. The stirring at the same temperature was
continued for 30 min, and then the reaction mixture was
saturated with (NH4)2SO4, and the target product was
extracted into ether. The ether extract was washed with
saturated solution of (NH4)2SO4 and dried over MgSO4.
The product was purified as described above.
b. At cooling 40% water solution of 0.01 mol of KOH
was mixed with 0.06 mol of 80% tert-butyl hydroperoxide.
At 3540°C while stirring was added dropwise within
3040 min 0.05 mol of glycidol. The stirring at the same
temperature was continued for 30 min. The separation
and purification of the product was performed as in
experiment a.
3-tert-Butylperoxy-1-methoxy-2-propanol (Va).
a. At stirring to 5 ml 0.5 N solution of sulfuric acid in
methanol heated at 3540°C was added dropwise within
3040 min 0.05 mol of peroxide Ia. Further workup
was carried out as described in the synthesis of com-
pound IV.
EXPERIMENTAL
b. At cooling 40% water solution of 0.01 mol of KOH
was mixed with 0.06 mol of 80% tert-butyl hydroperoxide.
At 3540°C while stirring was added dropwise within
3040 min 0.05 mol of glycidyl methyl ether. The stirring
at the same temperature was continued for 30 min. The
separation and purification of the product was performed
as in the synthesis of compound IV.
IR spectra were recorded on a double-beam spectro-
photometer IKS-14 (LiF prism). All measurement were
carried out at 293 K in a drop layer (condensed phase)
of nonfixed thickness; CCl4 was used as solvent.
1H NMR spectra were registered from solutions in
CDCl3 on a spectrometer Bruker at operating frequency
400 MHz in a pulse mode; internal reference TMS.
Compounds Vb and Vc were prepared in a similar
Initial epoxyperoxides Ia and Ib were prepared from
epichlorohydrin, the corresponding tert-alkyl hydro-
peroxides, and KOH as described in [1]. The content of
active oxygen was measured iodometrically.
way along both procedures.
Peroxide Vd was prepared only along procedure b
from tert-butyl glycidyl ether because in the acid medium
the tertiary alcohol added to the epoxy group only at the
temperature where the peroxy group might decompose.
3-tert-Butylperoxy-1-chloro-2-propanol (II). At
stirring to 0.05 mol of 3-tert-butylperoxy-1,2-epoxy-
propane (Ia) heated at 3540°C was added dropwise
within 3040 min 0.06 mol of concn. HCl. The stirring at
the same temperature was continued for 30 min, and then
the reaction mixture was diluted with a double volume of
the saturated water solution of (NH4)2SO4. The separated
organic layer was thrice washed with the water solution
of (NH4)2SO4 and dried over Na2SO4. The purification
of the product was carried out on a column packed with
Al2O3 of the II grade of activity using acetone as eluent.
3-tert-Butylperoxy-1-phenoxy-2-propanol (Ve).
At 4045°C while stirring was added to 40% solution of
0.56 g of KOH in water 0.15 mol of phenol. At the same
temperature was added dropwise while stirring within
3040 min 0.05 mol of peroxide Ia and within next
30 min 40% water solution of 2.24 g of KOH. The stirring
at the same temperature was continued for 30 min, and
then the reaction mixture was saturated with (NH4)2SO4,
and the target product was extracted into ether. The ether
extract was twice washed with 5% water solution of
NaOH, twice with water, and dried over Na2SO4. The
purification was performed as described above.
Similarly from 0.05 mol of epoxyperoxide Ia and
0.06 mol of 60% hydrobromic acid was obtained
compound III.
1,3-Di-tert-butylperoxy-2-propanol (VI).At cooling
40% water solution of 0.01 mol of KOH was mixed with
0.06 mol of 80% tert-butyl hydroperoxide. At 3540°C
1-tert-Butylperoxy-2,3-propanediol (IV). a. At
stirring to 5 ml 0.5 N sulfuric acid heated at 3540°C
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 11 2005
Elagin
